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Microstructures of W-Mo functionally graded material

L. M. ZHANG State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, Peoples Republic of China; Institute for Materials Research, Tohoku University, Katahira 2-1-1, Aobaku, Sendai 980-77, Japan H. P. XIONG State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, Peoples Republic of China; Welding Division, Beijing Institute of Aeronautical Materials, Beijing 100095, Peoples Republic of China E-mail: huaping.xiong@biam.ac.cn L. D. CHEN, T. HIRAI Institute for Materials Research, Tohoku University, Katahira 2-1-1, Aobaku, Sendai 980-77, Japan

Since the concept of functionally graded materials (FGM) was proposed, a great deal of research work on such a kind of advanced material has been done worldwide for different applications. It is also possible for the FGMs to be applied to dynamic high-pressure technology. Shock wave techniques offer unique capabilities for the experimental characterization of material properties at very high pressures and strain rates [1]. But the usefulness of the shock wave experiments can be expanded by using a kind of materials with a density gradient [2], from which extremely-high pressure can be offered at a much cooler temperature, and one can deduce some of the properties of different materials at the pressure and temperature. Recently, the application of graded-density layered materials in high-pressure technology has been reported [3]. However, they were only fabricated by bonding a series of thin plates such as Ta, Cu, Ti, Al, Mg and TPX-plastic, thus the density of the layered materials rises with great steps in the thickness direction. It is possible to produce a better effect if using a graded material with a continuous or quasicontinuous density change. R. Tu et al. [4] reported the fabrication of the kind of graded materials, Al-Cu system FGM, but such a FGM with a middle density should be improved. Moreover, it is necessary to investigate the graded material in a higher-density range, because for the ideal FGM with the density gradient to be fabricated, its density of one surface should be kept very low, while that of another surface should be kept as high as possible [2]. In fact, the thermophysical properties of W match well with those of Mo, and the brittleness of pure W and Mo themselves can be eliminated by using suitable elements as sintering additives. Moreover, according to the diagrams of W-Mo binary alloys, there is no trend to form brittle compounds between the two metals. The densities of pure W and Mo are high; that is, 19.3 g/cm3 and 10.22 g/cm3 respectively. Taking all of the previous factors into account, we chose the W-Mo system to investigate the FGM in the high-density range. This WMo FGM is one part of FGM with a wide density range we will fabricate in the future.
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Only when high relative density of every transient layer of such a FGM is ensured can good performance be obtained in factual application. The liquid-phase sintering method is usually applied to acquire tungsten heavy alloys with full density, but the corresponding sintering temperatures reach 16831793 K [57]. The research [8] on densication of tungsten refractories at lower temperatures is still insufcient. On the other hand, Mo bodies with nearly full density can be obtained at sintering temperature of 1573 K by using suitable additions [9]. In this paper, the authors initially chose the hot-pressing method and studied the densication of tungsten alloys at the low sintering temperature of 1573 K with Ni-Cu sintering aids. It was found through the supplementary experiments that the W-Mo alloys and Mo alloy also can be densied under the same sintering conditions. On this basis, we fabricated the dense W-Mo system FGM, focusing on discussing the formation of microstructures in the W alloy and W-Mo alloys as well as the W-Mo FGM. The fresh powders of W, Mo, Ni, and Cu with average particle size of 1.7, 2.4, 20 and 16 m respectively were used. The powders were mechanically mixed in the designed ratio, and blended for enough time to make them homogeneous. Then, the mixture was put into a cylindrical graphite mold, and hot-pressed in a furnace with a owing argon atmosphere. An initial pressure of 5 MPa was exerted on the powder mixture at room temperature. The temperature was increased to 1573 K at a rate of 15 K/min. Concurrently the pressure was also increased to 30 MPa. For all samples, the sintering temperature of 1573 K and the pressure of 30 MPa were held constant for 1 h. The total size of the sintered compact is 26 mm in diameter and about 3 mm in height. The density was measured by the waterimmersion technique. The microstructures of W95Ni3 Cu2 (wt. pct) alloy and Mo76W19Ni3Cu2 (wt. pct) alloy were observed and the corresponding element area distribution of elements Ni, Cu and elements W, Mo was determined respectively by scanning electron microscopy (SEM) with an X-ray length wave dispersion spectrometry (XRWDS). In preparing the W-Mo
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T A B L E I Comparison of the theoretical densities with the measured densities of some W-Mo alloys sintered at 1573 K with the sintering aids of Ni3-Cu2 (wt. pct) Weight ratio of W to Mo W alloy W/Mo = 4 : 1 W/Mo = 3 : 2 W/Mo = 2 : 3 W/Mo = 1 : 4 Mo alloy Theoretical density (g/cm3 ) 18.24 15.73 13.83 12.34 11.13 10.15 Measured density (g/cm3 ) 18.10 15.65 13.79 12.32 11.07 10.10 Relative density 99.2% 99.5% 99.7% 99.8% 99.5% 99.5%

Figure 1 Change of the relative density of sintered tungsten alloys with Cu content (content of Ni is xed at 3 wt.%).

system FGM, nine transient layers were inserted between the W side and the Mo side, in which the weight ratio of W to Mo was changed successively, and the thickness of each W-Mo transient layer was xed at 0.12 mm. The line distribution of elements W and Mo for the cross-section of the W-Mo FGM was also examined by XRWDS. 3 wt.% Ni was initially used for sintering of the tungsten alloy at 1573 K. The relative density of the W97Ni3 (wt. pct) alloy is 95.7%. To improve the relative density, in further sintering experiments Cu was added into the W-Ni alloy. The results reveal that the alloys relative density is obviously improved with the addition of Cu when Cu content is not very high (2 wt. pct) (refer to Fig. 1). Fig. 2 shows the microstructure (a) of the W95Ni3Cu2 alloy and the area distribution images of the elements Ni (b) and Cu (c). The distribution of Ni is similar to that of Cu, indicating that during sintering the liquid Cu dissolved part Ni. During sintering, Cu powders rst melted when they were heated to the melting point, 1356 K, and then, when further increasing the temperature and holding it at 1573 K, part of the Ni powders adjacent to Cu are dissolved into the liquid Cu. The owing of the liquid made it easy for Ni dissolved in the liquid to contact with W particles. Consequently, the dissolved Ni displayed more acti-

vating features during sintering than the solid Ni. The relative density of the tungsten alloy with additives of Ni3-Cu2 (wt. pct) reaches a maximum value of 99.2% at the low sintering temperature of 1573 K. However, further increasing the amount of Cu conversely results in decreasing of the relative density of the tungsten alloy. According to a previous analysis [10], the sintering activator Ni concurrently dissolved Cu and W during the sintering of the W-Ni-Cu alloys. With the increase of Cu content, Ni dissolved more Cu, while the solubility of W in Ni was reduced [10], which signies that the activation capability of the Ni was lessened, thus decreasing the relative density. In succeeding sintering experiments of W-Mo alloys and Mo alloy, the same additives of Ni3-Cu2 (wt. pct) were used. The microstructure of the W-Mo alloy and the area distribution images of elements W and Mo are presented in Fig. 3a, b, and c respectively. It can be seen that at the low sintering temperature, mainly the mechanical mixtures of W and Mo are formed. Good coherence between W grains and Mo grains is achieved because of the sintering additives, and because the solid solution of (W, Mo) is produced slightly at the W-Mo boundaries. The theoretical density of every W-Mo transient layer was calculated according to volume mixing rule. Table I compares the theoretical densities with the measured densities of some WMo graded layers, specifying that the relative density of

Figure 2 The microstructure (a) of the W95Ni3Cu2 alloy and the area distribution images of elements Ni (b) and Cu (c).

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Figure 3 The microstructure (a) of Mo76W19Ni3Cu2 alloy and the area distribution images of elements W (b) and Mo (c).

every graded layer is higher than 99.0%; i.e., all sintered W-Mo graded layers can be densied with the same sintering additives. It is worth noticing that the theoretical density of the (W, Mo) solid solution is higher than that of the mixture of W and Mo if adequate solid-solution reaction is occurred in W-Mo alloys at high enough temperatures. For example, the theoretical density of the Mo80W20 (wt. pct) alloy reaches 12.10 g/cm3 [11] when W and Mo in the alloy exist in the form of solid solution of (W, Mo). Based on this theoretical value, the theoretical density of the Mo76W19Ni3Cu2 (wt. pct) alloy can be calculated, and it shows the value of 11.89 g/cm3 . However, this theoretical density value was not achieved in the present paper. A fully dense W-Mo FGM can be fabricated since the W-Mo alloys in different weight ratio and with high relative density have been obtained under the same hotpressing conditions. Fig. 4 shows the second electron image (SEI) (a) of the fabricated W-Mo FGM and the line distribution images of elements W (b) and Mo (c) in the thickness direction. With the converse change of W content and Mo content in the thickness direction, the FGM factually exhibits a density gradient. It is interesting to notice that the etched extent of the FGM surface also changes evenly in the thickness direction under the same etching conditions (shown in Fig. 4a). Due to the gentle composition gradient in the FGM, the microstructures from the Mo side to the W side are also changed gently, i.e. there exists only a slight difference in the microstructure between any two adjacent graded layers. Fig. 5 presents the microstructures of micro-zones every 300 m interval from Mo to W in the thickness direction. Obviously, not only the microstructure but also the grain size are gradually varied, the latter rst being decreased and then increased. It is known that the sintering of W or Mo is accompanied with the inter-annexing of different grains and so with the growth of the grains. While in the case of W-Mo mixed layers, the growth of W or Mo grains would be restrained by the adjacent Mo or W grains respectively; i.e., in W-rich or Mo-rich zones, the normal grain growth still occurred, but at the boundaries be-

tween the two kinds of grains, the limited solid-solution reaction rather than the inter-annexing of grains occurred, and so the grain growth is halted there. As a consequence, the nal size of W or Mo grains becomes smaller. The closer the Mo content and the W content

Figure 4 The SEI (a) of the W-Mo system FGM and the line distribution of element W (b) and Mo (c) in the thickness direction (polished and etched).

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Figure 5 Microstructures of micro-zones in the W-Mo FGM every 300 m interval from Mo to W.

are, the more remarkable the phenomenon of grain growth being restrained, and this explains why the grain size changes as described previously in the thickness direction. In conclusion, under hot-pressing conditions of 1573 K30 MPa1 h, high relative density of the tungsten alloy was obtained by adding Ni-Cu sintering aids. The tungsten alloy, the molybdenum alloy and the W-Mo alloys were concurrently densied with the same sintering additives of Ni3-Cu2 (wt. pct). It is found that at the sintering temperature of 1573 K, mainly the mechanical mixtures of W and Mo are formed in the W-Mo alloys, and the solid solution of (W, Mo) is produced slightly at the W-Mo boundaries. Finally, a fully dense W-Mo FGM was successfully fabricated, in which not only the microstructure but also the grain size are gradually varied in the thickness direction. The latter is rst decreased, and then increased.

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Acknowledgment This research is sponsored by National Natural Science Foundation of China (No. 59771028).

Received 27 August and accepted 10 December 1999

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